Olefin oxide polymerization catalysts



United States Jersey No Drawing. Filed June 24, 1959, Ser. No. 822,413 4 Claims. (Cl. 260-439) This invention relates to a new catalytic material suitable for effecting the polymerization of olefin oxides, to the method of preparing such catalyst and to the method of utilizing the catalyst in conducting the polymerization of olefin oxides. The catalytic material more particularly is a complex resulting from the reaction of a ferric halide with cyclododecatiiene-l,5,9.

It is known that ferric chloride will catalyze the polymerization of olefin oxides. However, the reaction takes place so rapidly as to be essentially explosive and hence is practically uncontrollable. The present invention provides a new catalyst system for this type of polymerization reaction which permits the reaction to be conducted under controllable conditions.

According to the invention a. catalyst is prepared by reacting either FeCl or FeBr, with cyclododecatriene- 1,5,9 which, for the sake of brevity, is hereinafter sometimes referred to as CDT. The latter compound can be prepared in a known manner, such as by contacting butadiene with a catalyst formed from titanium tetrachloride and diethyl aluminum chloride in a hydrocarbon solvent. It has now been discovered that CDT will react with ferric chloride or bromide to form an iron-containing complex which will catalyze the polymerization of olefin oxides in a controllable manner. Hydrogen halide is also formed as a product of the reaction, and it has further been discovered that removal of the hydrogen halide from the complex greatly improves its activityas a polymerization catalyst.

The reaction product of the ferric halide with CDT is a dark solid material having a composition that has not been determined with certainty thus far. However, tests have indicated that it includes a crystalline component having the empirical formula FeX- (CDT), wherein X represents chlorine or bromine, in admixture with FeX and possibly also with unreacted FeX At least 70% of "the iron in the product appears to be in the ferrous state.

The above-described catalytic product can be prepared simply by adding CDT to anhydrous FeCl;, or FeBr The reaction takes place quite readily at room temperature and is highly exothermic. An organic solvent such as chloroform, carbon tetrachloride, diethyl ether, pentane, hexane and the like can be included in the reaction mixture if desired, although this is not essential. After the reactants have been mixed and the exotherm is complete, it is preferable to heat the mixture for a time, for example to a temperature in the range of 60-100 C. for a time of to 60 minutes. Thereafter, the reaction mixture is placed under a vacuum until all of the volatile material has been vaporized. This removes HCl formed as a result of the reaction and improves the catalytic activity of the product. This procedure yields a dark atent solid material which constitutes the catalyst of the present invention.

The catalyst is effective for polymerizing any olefin oxide, such as ethylene oxide, propylene oxide, chloropropylene oxide, isobutylene oxide, styrene oxide and the like. The polymerization can be carried out at temperatures in the range of 0150 C., with the reaction rate increasing as the temperature is increased. A solvent such as pentane, hexane, isooctane, benzene, toluene, petroleum ether or diethyl ether can be used if desired, although the use of a solvent is not required. The resulting polymerization product is a mixture of amorphous and crystalline polymers which are easily separable from each other by meansof cold acetone, the amorphous material being soluble therein while the crystalline material is insoluble when the temperature of the acetone is below about 20 C. The amorphous polymer is an oily material suitable for use as a synthetic lubricant, andthe crystalline material can be utilized to make molded articles, fihns and the like.

The following example is a specific illustration of the invention:

A catalyst is prepared by adding 15 ml. of CDT'to 5.0 g. of anhydrous FeCl at room temperature in a polymerization tube. After the exothermic reaction has stopped, the mixture is heated at 70 C. for about 30 min utes. The mixture is then placed under a vacuum until the HCl has been removed from it. 125 g. of propylene oxide are added to the tube and the mixture is gently agitated at room temperature for 96 hours. At the end of this time, 2500 ml. of acetone are added and the mixture is chilled to a temperature of about -25 C. The in- I halide is FeCl 3. Method of preparing a catalyst suitable for the polymerization of olefin oxides which comprises reacting a ferric halide selected from the group consisting of FeCl, and FeBr, with cyclododecatriene-1,5,9 and removing from the product HCl resulting from the reaction.

4. Method according to claim 3 wherein the ferric halide is Fecl References Cited in the file of this patent UNITED STATES PATENTS 2,849,471 Thomas Aug. 26, 1958 2,870,101 Stewart Jan. 20, 1959 2,873,258 Borkovec Feb. 10, 1959 2,898,360 Hogan et al Aug. 4, 1959 

1. A CATALYST FOR THE POLYMERIZATION OF OLEFIN OXIDES CONSISTING ESSENTIALLY OF A COMPLEX FORMED BY REACTING A FERRIC HALIDE SELECTED FROM THE GROUP CONSISTING OF FECI3 AND FEBR3 WITH CYCLODODECATRIENE-1,5,9 AND REMOVING HCL RESULTING FROM THE REACTION. 